Manufacture of ethyl alcohol



Patented Oct. 23, 1934 EN -fir MANUFACTURE .oF ETHYL ALCOHOL WalterPhilip Joshua, London, Herbert Muggleton Stanley, Tadworth, and JohnBlair Dymock; Cheam, England, assignors to The Distillers CompanyLimited, Edinburgh,

British company- Scotland, a

No Drawing. Application Januar 11. 1933, 5 Serial No. 651,222. In GreatBritain March 10,

7 Claims. (01. 260-156) ,1

The present invention relates to the production ofethyl alcohol by thedirect combination of ethylene with water vapor. 1

It is well knownthat water vapor and ethylene will combine with theformation of ethyl alcohol at high temperatures and without the presenceof substances having a catalytic effect on the reaction but the amountof conversion is negligible. A number of catalysts have been proposedfor use in this reaction such as for example thoria or phosphoric acidon charcoal.

According to the present invention, ethylene and water vapor are causedto combine at high temperatures at atmospheric or increased pres- I5phosphate of the iron but not in excess of about 95 per cent. of thecatalyst composition.

The catalyst so compounded may be used as such in the solid state in theform of granules, pellets, tablets and so forth or may be supported onor admixed with inert carriers, but excluding silicious compounds, orthe carriers may be impregnated with the catalyst in fluid form and usedin such condition or may be subsequently dried. In the case of thosecompositions of catalyst in which the latter becomes fluid'under theoperating conditions it may be used in that form, and in such caseethylene and water vapor may be passed through the catalyst. Thecatalyst may be used alone or in conjunction with other materials knownto have a favorable catalytic effeet on the combination of steam andethylene.

The reaction may be carried out at temperatures from 100 to 300 C., butwe prefer to use temperatures above 150 C. Atmospheric pressure may beemployed or increased pressures up to 250 atmospheres, but we prefer touse pressures not exceeding 100 atmospheres.

In carrying out the operation a mixture of ethylene and steam insuitable proportions is brought into contact with the catalyst and theresultant vapors are thereafter condensed to separate the ethyl alcoholproduced together with unchanged water vapor, and the unchanged ethyleneis returned to be retreated.

The catalyst may be prepared by treating with phosphoric acid the oxide,oxalate, carbonate, or other compound of iron decomposable by phosphoricacid.

The process may be applied to pure ethylene or to mixtures of ethylenewith gases which are not reactive under the conditions of the e. g.ethane, methane'and the like. f The followingexamples-illustrate themanner in which the invention maybe carried into effect and the natureof the results obtained:-

A group of four catalysts was first prepared from ferrous oxalate andphosphoric acid and dried at 200 C. in an air oven, the ratio of ferrousoxide to phosphoric acid in the finished products being represented bythe formula given below:

(1) FeO, 2H3PO4 (2) FeO, 2.5H3PO4 (3) FeO, 2.7H3PO4 (4) FeO, 3H3PO4Example I When working under atmospheric pressure conditions, 100 cc. ofeach catalyst was employed at a temperature of 200 C. and ethylene atthe rate of 3.12 litres per hour measured at N. T. P. was passed inadmixture with 1.5 times its volume of steam over each catalystseparately. The results were as follows:--

process,

Conversion 0 Catalyst ethylene 0 ethanol Percent (1) F90, 2H3P04 0. 41(2) FoO, 2.5HaPO4- 0. 69 (3) F90, Z.7H3PO4 0.56 (4) FeO. 3HaPO4. 0.40

Example II was 0.83 per cent. and the hourly output of alcohol was 6.78grams. The alcohol was obtained in the form of an 8.4% condensate.

Example III In a further experiment carried out under a total pressureof 40 atmospheres the volume of ethylene calculated at N. T. P. passingper hour over the same volume of catalyst (maintained at 280 C.) was1260 litres mixed with steam in the molar proportions of 7 mols.ethylene to 1 mol. steam. The conversion of ethylene to ethanol was 0.67per cent. and the hourly output of alcohol was 17.4 grams. The alcoholwas obtained in the form of a 10.8% condensate.

What we claim is:

l. The production of ethyl alcohol comprising directly combiningethylene with water vapor at elevated temperature in the presence of acatalyst compounded from phosphoric acid and ferrous iron, the amount ofphosphoric acid present in the catalyst being in excess of that requiredto form the ortho-phosphate of iron but not in excess of about 95 percent. of the composition.

2. The production of ethyl alcohol according to claim 1, in which theoperating temperature employed lies between 100 C. and 300 C.

3. The production of ethyl alcohol according to claim 1, in which theoperating pressure is atmospheric.

4. The production of ethyl alcohol according to claim 1, in which thepressure employed is superatmospheric up to about 100 atmospheres.

5. The production of ethyl alcohol according to claim 1, in which theethylene used is in admixture with a gaseous medium that is not reactiveunder the operating conditions.

6. The method of producing ethyl alcohol comprising combining ethylenewith water vapor in the presence of a catalyst compounded fromphosphoric acid and ferrous iron in order to form the orthophosphate ofiron, the amount of phosphoric acid present in the catalyst being inexcess of the stoichiometric quantity but not in excess of about 95% ofthe composition.

'7. The method of producing ethyl alcohol comprising combining ethylenewith water vapor in the presence of a catalyst comprising essentiallyphosphoric acid and a substance containing a substantial amount of ironin order to form the ferrous orthophosphate of iron, the amount ofphosphoric acid present in the catalyst being in excess of thestoichiometric amount but not in excess of about 95% of the composition.

WALTER PHILIP JOSHUA. HERBERT MUGGLETON STANLEY. JOHN BLAIR DYMOCK.

